Purity of DGA Normal for Po Separations

Daniel McAlister, Ph.D. Senior Chemist Ed Rush Chemist

www.eichrom.com

DGA Applications

2

N

O

O N

O

RR

RR

Rare Earth Separations1

Trivalent Actinides1

Removal of alpha emitters from Ra2

Polonium Separations3

1Horwitz, McAlister, Bond, Barrans, Jr., Solv. Extr. Ion Exch., 23, 319 (2005)2Maxwell, Culligan, Hutchinson, Utsey, McAlister, J. Radioan. Nucl. Chem. 300(3), 1159 (2014)3Mawwell, Culligan, Hutchinson, Utsey, McAlister, J. Radioan. Nucl. Chem. 298(3), 1977 (2014)

www.eichrom.com 310-1 100 101

100

101

102

103

104

105

106

HNO3

HCl

k' Po on DGA Resin

k'

[Acid], M

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DGA Quality Control

4

2009 and earlier: Elution of Eu-152 TracerPeriodic LC-MS

2010-2015: Separation of Am-241 and U-233

2015 and later: Add Po QC test

www.eichrom.com 5

DN

S09

2209

DN

S09

2409

DN

S02

1010

DN

S08

2610

DN

S03

0111

DN

S04

2211

DN

A04

2611

DN

S08

1511

DN

S10

1911

DN

S04

0312

DN

S09

2412

DN

S02

2513

DN

S05

1013

DN

S09

1613

DN

S10

2513

DN

S09

0614

DN

S11

1314

DN

S03

1415

DN

S05

0515

0

20

40

60

80

100

Po

Rec

over

y in

20m

L 0.

05M

HN

O3

Polonium Recovery on TODGA

Pur

ifica

tion

Only Po???

What Changed?Can we purify?

How do we prevent?

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Synthesis of DGA from Diglycolyl chloride (DGC)

7

O

O

ClCl

O

NHRR

+THF

NR'

R'R'

+

O

O

NN

O

RR

RR

NR'

R'R'HCl

Horwitz, McAlister, Bond, Barrans, Jr., Solv. Extr. Ion Exch., 23, 319 (2005)Sasaki, Sugo, Suzuki, Tachimori, Solv. Extr. Ion Exch., 19, 91 (2001)

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Raw Materials

8

Purchased a large amount of DGC in 2011- Synthesis Chemist noted darkening of material over time- Dark material was not a problem in the past- Dark material persists into final product- Impurity is heat/pH sensitive

Supplier began packing Dioctylamine in plastic (was glass)- Plastic containers frost over (amine + air/moisture)

Po issue not observed with TEHDGA- Is dioctylamine the source of the issue?

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Distill Diglycolylchloride

Improved Synthesis and Purification

9

Distill Dioctylamine

Test Po recovery.Additional purification as necessary.Full batch and standard QC.

Dry Solvent

www.eichrom.com 10DN

S02

1010

DN

S08

2610

DN

S04

2611

DN

S03

0111

DN

S04

2711

DN

S08

1511

DN

S10

1911

DN

S04

0312

DN

S09

2412

DN

S02

2513

DN

S05

1013

DN

S09

1613

DN

S10

2513

DN

S09

0614

DN

S11

1314

DN

S03

1415

DN

S05

0515

0.0

0.2

0.4

0.6

0.8

1.0

96.096.597.097.598.098.599.099.5

100.0

Am in U fraction

% A

m R

ecov

ery

Am Yield

Am in Standard DGA QC

www.eichrom.com 11DN

S021

010

DN

S082

610

DN

S042

611

DN

S030

111

DN

S042

711

DN

S081

511

DN

S101

911

DN

S040

312

DN

S092

412

DN

S022

513

DN

S051

013

DN

S091

613

DN

S102

513

DN

S090

614

DN

S111

314

DN

S031

415

DN

S050

515

0.0

0.2

0.4

0.6

0.8

1.0

96.096.597.097.598.098.599.099.5

100.0

U in Am fraction

% U

Rec

over

y

U Yield

U in Standard DGA QC

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Title and Content slide

12

DN

X030

27D

NX0

3277

DN

X041

17D

NX0

8177

DN

X082

47D

NX0

3278

DN

X040

98D

NX0

4148

DN

X052

08D

NX0

6138

DN

X061

68D

NX0

8050

9D

NX0

5120

9D

NX0

6100

9D

NX0

6160

9D

NX1

0120

9D

NX1

0120

9-2

DN

X101

309

DN

X101

409

DN

X093

110

DN

X090

110

DN

X060

611

DN

X071

911

DN

X090

512

DN

X060

313

DN

X080

114

DN

X042

115

0.1

1

10

100

Po (0.05M HNO 3) U (0.1M HNO 3) Am (3M HCl)

k'

k’ on DGA Resin Lots

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Title and Content slide

13

0 1 2 3 4 5 6 7 8 9 10 11101

102

103

104

105

dp

m C

f-252

mL 0.1M HCl

2010 (Good) 2015 (Worst) 2015 (Cleaned)

Elution of Cf-252 from 2mL DGA, Normal Cartridges

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0.01 0.1 11

10

100

k' -

Po

[HNO3], M

DNSR10A DNS031415 DNX100715 DNX073115

14

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Synthesis and Degradation of DGC

15

O

O

ClCl

O

O

O

OHHO

O

SOCl2 SO2 HCl

Aged samples of SO2Cl2 develop a yellow hue, possibly due to the formation of S2Cl2.

S2Cl2 has been used to introduce C-S bonds.

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Synthesis and Degradation of DGC

16

O

O

ClCl

O

O

O

OHHO

O

PCl3

PCl5 POCl3

H3PO4

HCl

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Synthesis and Degradation of Dioctylamine

17

n R OH NH3+ RnNH3-n H2O+

n R X NH3+ RnNH3-n nXH+ NH3

Octylamine impurity?

Hydrolysis/Oxidation by air/water?

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Common DGA Impurities by LC-MS

18

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Elemental Analysis of DGA Lots

19

Lot(74.4%)

C(12.5%)

H(8.3%)O

(4.8%)N S P

DNX090512(Good) 74.6 12.8 8.4 4.9 0.07 <25ppm

DNX060915(OLD DGC) 74.6 12.4 8.3 4.8 0.1 <25ppm

Impurity from Column 67.7 11.8 14.3 5.5 <0.05 <25ppm

DNX073115(NEW DGC) 74.8 12.9 8.4 4.8 <0.05 <25ppm

C = 67.4% O = 13.5%H = 11.3% N = 7.9%C = 67.0% O = 17.9%H = 11.0% N = 3.9%C = 69.4% O = 13.2%H = 11.6% N = 5.8%

O

N O

O

NHOOct

OctOct

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• DGA Synthesis and Purification Improved• DGA QC updated with Po testing• DGA lots from 2010-2015 tested retroactively

– Standard Separations– Po Separations

• Only separation affected by impurity – Other customer separations (as comments received)– Data available upon request

Summary

20